Metallisable azo dyestuffs and complex heavy metal compounds thereof



Unite METALLISABLE AZO DYESTUFFS AND COMPLEX HEAVY METAL COMPGUNDSTHEREOF No Drawing. Application March 3, 1955 Serial No. 492,047

Claims priority, application Switzerland March 5, 1954 8 Claims. (Cl.260-151) The present invention concerns the production of newmetallisable azo dyestuffs and the complex heavy metal compoundsthereof, in particular of the blue-green to yellow-green, often verypure, complex chromium compounds. It also concerns their use for theattainment of very fast dyeings on textiles, for the dyeing of lacquersor films as well as the fast dyed material so obtained.

It has been found that valuable metallisable azo dyestuffs are obtainedby diazotising an aromatic amine which, in the neighbouring position tothe amino group contains a substituent capable of forming the metalcomplex or a substituent which can be converted into a metallisablegroup or substituents which can be exchanged therefor. This aromaticamine is then diazotised and 'coupled with a Z-arninonaphthalenecompound coupling in the 1-position which is substituted in the aminogroup by an organic radical, which latter contains a substituent.capable of taking part in the complex formation. The dyestuffs soobtained can be converted with agents giving off metal either on thetextile fibre or, preferably, in substance, if desired after or whileconverting or exchanging one of the substituents of the diazo componentin the o-position to the azo linkage into or for a metallisable group toform valuable heavy metal containing dyestulfs.

Diazotised aromatic amines of the isocyclic as well as the heterocyclicseries are suitable diazo components for the production of the newdyestuffs. Chiefiy the diazoxides of the benzene series which areadvantageously negatively substituted and preferably by nitro groups,can be used as diazo components. As amines can be named:-nitro-4-methylor -4-chloro-2-amino-1-hydroxybenzene, 5- or 4 nitro 2amino 1 hydroxybenzene, 4.6- dinitro 2 amino l hydroxybenzene, 6 nitro4- chloroand 4 nitro 6 chloro 2 amino l hydroxybenzene. 4 nitro 6acetylaminoand 6 nitro- 4 acetylamino 2 amino l hydroxybenzene, 6- nitro4 methylor -4 tert. butylor -4 tert. amyl- 2 amino 1 hydroxybenzene; 5-or 6 nitro 4 alkylsulphonylor alkenylsulphonyland 4 nitro 6alkylsulphonylor alkenylsulphonyl 2 amino 1 hydroxybenzenes, 6 nitro 4acyland 4 nitro 6 acyl 2- amino 1 hydroxybenzenes, 6 nitro 2 amino 1-hydroxybenzene 4 sulphonic acid amides and 4 nitro 2 amino lhydroxybenzene 6 sulphonic acid an1- ides and derivatives thereofsubstituted organically in the atent ice amide group. However, also 4-or S-alkylsulphonyL'aL kenylsulphonyland arylsulphonyl 2 amino 1-hyndroxybenzenes tas=well as 4- or 5-acyl-, e. g. the 4- or 5-acetyl-,propionyl-, or butyryl 2 amino 1 hydroxybenzenes, 3.4.6 .trichloro-Z--amino 1 hydroxybenzene, -4 nitro 2 --amino -1 hydroxybenzene 5- or -6-sulphonic acids, 6 -.nitro 2 amino 1 hydroxybenzene 4 sulphonic acid, 2amino 1 -hydroxyben- -zene 4 -.phenylsulphone 3' sulphonicacid, 2 amino-1 hydroxybenzene 4 sulphonic acid N ethylanilide- 4" -sulphonic ac id, 4chloro 5 nitro 2 amino 1- hydroxybenz ene '6 -.sulphonic acid, 3.4dichloro -'5- nitro, -2 amino 1 hydroxybenzene 6 sulphonic acid or 6nitro 2 --amino 1 hydroxybenzene --4- carboxylic acid aswell as 4 nitro2 amino --1 -'hy ,droxybenzene 6 carboxylic acid can be used.

Other .o-aminophenols 0r o-aminonaphthols' the diazoXides of which haveinsuflicientcoupling energy can be acylated at the hydroxyl group, e. g.with p toluene-sulphonic-acid chloride, rbefore the diazotisation.Theycan then be diazotisedand coupled whereuponathe acyl radicalinthedyestufi formed is'againtsplit oft. *Finally,=also diazotised primaryaromatic aminescan be .used which contain in the o-position to the.diazotised :amino group zene, 2.5 dimethoxy 1 -aminobenzene,'5 ethoxy-2- methoxy 1 aminobenzene, 1 amino 2 methoxy -"-5- chlorobenzene, aswell as o-alkoxyaminobenzene sulphonic acids can be-used.

Examples of diazo components of'theheterocyclic series are: 1 amino 2hydroxy 5:4 -hydroxyme'thyl- .ene'sulphone, 1 amino- 2 methoxy 5.4hydroxymethylene sulphone,-2 --amino 3 hydroxy -6 a chlorophenoxthine Sdioxide, 2 --amino 3 methoxy -6- chloro phenoxthine -S dioxide, 2- amino"3 hydroxy 6 methylsulphonyl phenoxthine S dioxide, 2 amino 3 methoxy 6methylsulphonyl 1phenoxthine-S-dioxide. Such compounds are obtained forexample-by the addition of u-halogenalkyl sulphinicacidslor o-halogen'phenyl sulphinic acids to benzoquinone and thensplitting off hydrogenhalidewhile closing rthe ring in the presenceofacid'binding agents,nitrating, .ifnecessary methylating the hydroxyl; group and reducingrthcnitrogroup. to the amino-group.

Compounds which. can be used as. N-substitutedlrami nonaphthalenecompounds coupling in the 1-position which have asubstituent in theorganic radical ofthesecondary amino .group taking. part in thecomplexformation are thosewhifch in an aor 5-. positioncf this radicalcontain one of the usual rnetallisable substituents, e. g. acarboxylgroup, a hydroxyl group, an amino group,

an acylamino group, a sulphonic acid amide group which can be derivedfrom ammonia or a primary organic amine, a sulphonic acid carbacyl amidegroup or a carboxylic acid alkyl or aryl sulphonyl amide group. The ,8-CH COOH radical, the fi-aminoethyl radical, an alkylsulphonylor anarylsulphonyl-Z-aminoethyl radical and, preferably, a phenyl radicalcontaining one of the metallisable substituents listed above in the2-position and which can contain other substituents usual in azodyestuffs, e. g. alkyl, alkoxy, sulphonic acid, carboxylic acid,sulphonic acid amide, (N-substituted included), nitro, acylamino,alkylsulphonyl groups and halogens are examples of substituents in theN-position of the Z-aminonaphthalene coupling component. The2-(2'-carboxyphenylamino)-naphthalene compounds are particularlyadvantageous because they produce particularly pure complex chromiumcompounds and because they are technically easily available, e. g. fromZ-aminonaphthalene and derivatives thereof with a free, unhinderedl-position and Z-aminobenzene-l-carboxylic acids according to Bucherersmethod. They can also be obtained from 2-chloroor2-bromo-benzene-l-carboxylic acids by condensation while splitting offhydrogen halide. Suitable coupling components from these preferredgroups are for example, the following unsulphated compounds: 2 (2'-carboxyphenyl) aminonaphthalene, 2 (2' carboxyphenylamino) 6methoxynaphthalene, 2 (2' carboxyphenylamino) 7 methoxynaphthalene. 2(2'- carboxyphenylamino) 8 methoxynaphthalene, 2 (2'-carboxyphenylamino) methoxynaphthalene, 2 (2'- carboxyphenylamino) 6bromonaphthalene, 2- (2'- carboxyphenylamino) 6 tert. butyl naphthalene.2 (2'- carboxyphenylarnino) naphthalene 5- or -6- or -7 sulphonic acidamide or N-methylamide, 2 (2' carboxy- 5' chlorophenyl)aminonaphthalene. 2 (2' carboxy- 4' acetylaminophenyl) aminonaphthalene.The following can be named as representative sulphated couplingcomponents: 2 (2' carboxyphenylamino) naphthalene S sulphonic acid. 2(2' carboxyphenylamino)- naphthalene 6 sulphonic acid or 2 (2'carboxyphenylamino) -naphthalene-7-sulphonic acid.

The diazo components usable according to the present invention arediazotised according to the usual methods in aqueous or organic aqueousmineral acid solution or suspension with sodium nitrite in the cold. Thecoupling is performed in a neutral, weakly acid or also stronger acidmedium if necessary while gradually adding acid buffering agents such assodium acetate. It is often advantageous to performthe coupling at atemperature higher than usual, e. g. at 40-80 C.,often advantageously inthe presence of stabilisors for the diazo compound,

e. g. in the presence of naphthalene monoor di-sulphonic acids or oftetraline sulphonic acids.

Generally the dyestuffs according to the present invencolour. Theconversion into the metal complexes can be done according to the usualmethods in aqueous solution or suspension or, often with advantage,according to the composition, in organic solution, by heating in openvessels under reflux or in closed vessels under pressure. Compoundscontaining trivalent chromium or cobalt, nickel, iron, manganese, can beused as agents giving off metal such as the normal or complex salts ofthese metals, and also the hydroxides can be used. Due to their oftenvery pure green-blue, green to yellow-green and olive shades, thecomplex cobalt and particularly chromium compounds are suitable for thedyeing of natural and synthetic polypeptide fibres. In addition they canalso be used, as can also the complex metal compounds of other metals,for the dyeing of cellulose esters in the mass and for the production ofdyed films.

An advantage of the monoazo dyestulfs according to the present inventionis that they can be converted particularly easily into complex metalcompounds which contain one heavy metal atom per dyestufi molecule boundin complex linkage. These are often distinguished by particularly pureshades. Although such types can be obtained particularly easily fromusual sulphated ohydroxy-o-aminoazo dyestuffs for example with chromicsalts of stronger acids by boiling in aqueous solution, analogousdyestuffs without sulphonic acid groups can be obtained in this way inaqueous medium only with very great difficulty and the yields and thepurity thereof are unsatisfactory. In contrast to this, because of theirgreater tendency to form metal complexes and the stability of the metalcomplexes containing one heavy metal atom in the dyestuff molecule, thedyestuffs according to the present invention can be converted into themetal complexes of the type described above in an aqueous medium, evenwhen there are no sulphonic acid groups present.

The following examples illustrate the invention without limiting it inany way. Where not otherwise stated, parts are given as parts by weightand the temperatures are in degrees Centigrade. The relationship ofparts by weight to parts by volume is as that of kilogrammes to litres.

Example] 7 COOK OH NH parts of sodium intrite.

a red powder which is easily converted into the water soluble" sodiumsalt by mixing with sodium carbonate. Wool 1 s dyed according to themetachrome process in pure yellowish-green shades.

Example 2 Chromium complex compound a 23.2 parts of S-nitro-Z-amino 7 1hydroxybenzene 4'- methyl sulphone in parts of water are dissolved with10 parts by volume of 10 N-caustic soda lye, 6.9 parts of sodium nitriteare added and the whole is added dropwise at 0 to a solution of 31 partsof Z-naphthalene sulphonic acid in 200 parts of water. The suspension ofthe yellow diazoxide is poured into a paste of 27.6 parts of2-(2'-carboxyphenyl)-naphthylamine in 200 parts of glacial acetic acidand stirred at 70-80 until completion of the dyestufi formation. Thedyestufi is filtered oil and then washed first with acetic acid and thenwith hot water. The dried colour acid in 400 parts of ethylene glycol isdissolved with 20 parts by volume of N- caustic soda lye and heated to120125 with 28 parts of chromic acetate (corresponding to 5.72 parts ofchromium) until the starting dyestufi has disappeared. The greenchromium containing dyestufi is precipitated by pouring into sodiumchloride solution and it is filtered oflz. After drying, it is a darkgreen powder which, after mixing with sodium carbonate, dissolves inwater. It dyes wool from an acetic acid bath in pure green shades whichhave very good fastness properties.

A similar dyestufi is obtained if, instead of 27.6 parts of2-(2-carboxyphenyl)-naphthylamine, 31.2 parts of 2-(2'-carboxy-5'-chlorophenyl)-naphthylamine are used.

Example 3 COOH Chromium complex compound 18.9 parts of5-nitro-4-chloro-2-amino-1-hydroxybenzene are diazotised as described inExample 1 and coupled with 27.6 parts of2-(2'-carboxyphenyl)-naphthylamine. The dyestuft so obtained is pastedin 300 parts of ethylene glycol monomethyl ether and boiled under refluxwith 32 parts of chromic acetate (corresponding to 9.2 parts of Cr Ountil the metallisation is complete. The metal containing productisdiluted with water and the precipitated chromium complex is filteredoff. After drying, it is a green powder which is soluble in hot waterafter being mixed with substances having an alkaline reaction. It dyeswool from a weakly acid bath in green shades.

Example 4 CODE Chromium complex compound 22.9 parts of2.5-dimethoxy-l-aminobenzene-4-methyl sulphoue in 150 parts of water aredissolved -with 29 parts of concentrated hydrochloric acid anddiazotised at 0-5 with 20.7 parts of a 33% sodium nitrite solution. Theyellow diazonium solution is poured into a solution of 27.6 parts of2-(2-carboxyphenyl)-naphthyl- 6 amine in 200 parts ofethyleue glycolmonomethylether, 28 parts of crystalline sodiumracetate are added andthe whole is stirred until thedyestuff formation is complete. Thedyestuif is filteredofi and. after drying, is heated in -400-parts offormamide to 150: with 32 parts of-chromic acetate (corresponding to9.2:parts ofcr O until the starting dyestuif has disappeared. The stillhot chroming mixture is poured into 1000 parts of saturated sodiumchloride solution and the precipitated dyestufi is filtered off. Aftermixing with substances having an alkaline reaction, it is soluble inhotwaterand-it dyes-wool from aweakly acid bath in bluish-greenshades.

Example 5 Co OH soicm Cobaitcomplex compound 23.2 parts of5-nitro-2-amino 4 1 hydroxybenzene-4- methyl sulphone are diazotisedaccording to Example 2, and coupled with 27.6 parts of2-(2'-carboxyphenyl)- naphthylamine. The isolated colour acid in 500parts of hot water is dissolved in 10 parts by volume of 10 N-causticsoda lye and heated for 3 hours at -90 with .120 parts of a solution ofcobalt .aetat'etcorresponding to 7.1 parts of cobalt). The cobaltcomplex is completely precipitated by the addition of sodium chlorideand is filtered oil. After mixing with substances having an alkalinereaction, it is soluble in hot water and it dyes wool from a weakly acidbath in olive green shades.

Example 6 COOH I SQz-NQ-SOaH Chromium complex compound 37.2 parts of2-amino-1-hydroxybenzene-4-sulphethyl anilide-4'-sulphonic acid arediazotised according to Example 2 and coupled at 40-50 with 27.6 partsof 2-(2'- carboxyphenyl)-naphthylamine. The dyestuff is isolated by theaddition of sodium chloride solution. It is dissolved in 750 parts ofwater and boiled under reflux with 300 parts of a solution 'of chromicsulphate (corresponding to 11.5 parts of Cr O until the startingdyestuflihas disappeared. After drying. it is a green powder which dyeswool from a strong sulphuric acid bath in green shades.

The following dyestuffs can also be produced according to the aboveexamples:

No. Dlazo component Azo component metal colour on wool-i-n.itro-2-amino-1-hydroxybenzene 2-(2'-carboxyphenyl)-naphthylamlne Orgreen. 4.6-dlnitro-2-amiuo-l-hydroxybenzene I Gr yellowish green.

2-amlno-1-hydroxybenzene-4-phenyl sul- I 7 01' green..

phoue-3-sulphamide. S-nitro-2-amino-lrhydroxybenzenel-methyl2-(2-carboxy-4'-acetylamlnophenyl)-naphafter chromed sulphone.thylamine. green. 5-nitro-2-amino-1-hydroxybenzene 2 (2 acetylamino 4'methylsulphonyl- Or grey-green.

' phenyD-naphthylamine. do 2 (2' amino 4 -methylsu1phonylphenyl)- Or Do.

naphthylarnine. do 2 (2' carboxyphenyl) naphthylamlne- 6- Or green.

sulphonic acid.

E-nligo4chloro-2-amino-l-hydroxybenzene- Z-(B-aminoethyl)naphthylamimfGr bluish-green.

fi-nliltro-2-arglno-1-hydroxybenzene-4-sul-2-(2-earboxyphenyl)maphthylamin Or green pOnlCacl.

2 amino l hydroxyhenzene 4-sulphonio do Cr Do.

acid-(ii-chlorsnillde). p

4-nitro-2-amino-I-hydroxybenzene 2- (2'-amino-4'-methylsulphonylphenyl)- Cr 7 grey-green.

naphthylamine. t 13 do 2 (2 acetylamino 4' methylsulphouyl Or Do.

phenyD-naphthylamine. 5-nitro-2-amino-1-hydroxybenzcne-4-ethyl 2- (5'-chloro 2' -carboxyphenyl) -naphthy1- Cr yellowish green.

sulphone. amine. a

4.G-dinitro-2-amluo-1-hydroxybenzene 2-(fi-oarboxyethyl)-naphthylaminegreen: 5-nitro-2-amino-l-hydroxybenzeneZ-(5-an1inoethyl)-napl1thylamine. bluish green. 2 amino l hydroxybenzene4 sulphethyL 2-(2' -oarboxyphony1)-naphthylamine Co green.anilide-3'-sulphamide. I r 5-nitro-2-amino-1-hydroxybenzeue 2 (2oarboxyphenyl) naphthylamine 7 Or Do.

sulph onic acid. Z-amiuobenzoic acid methyl ester. r2-(2-oarboxyphenyl)-naphthylamine Cr blue-green. o-nitro r raminobenzoieacid o ,Gr Do. 2 alrlnino o hydroxybenzene 4 -methylsul-2-(fl-hydroxyethyD-naphthylamlne Or "Do.

p one. S-nitro-2-amino-l-hydroxybenzene-4-methdo Cr Do.

ylsulphone. 23 d0 a v 2- (2'-tolylsulpham1do-4'-methylsulphonyl)- Orolive grey.

naphthylamine. 24 6-n1tro-2-amino-1-hydroxyhenzene 2 (2'mcthylsulphamido 4' methylsul- Or Do.

phonyD-naphthylamine.

What I claim is: 3. A dyestufi selected from the class consisting of thel. A dyestuff selected from the group consisting of monoazo dyestufishaving the formula: the monoazo dyestufis having the formula: I

wherein A represents a mononuclear carhocyclic aryl radical, Xrepresents a metallisable group in the o-position to the az'o groupselected from the group consist- 5 ing of OH and 'COOH, andthechromium'complexes of said dyestuffs.

4. The complex chromium compound of a'monoazo dyestufi having theformula:

wherein A represents a mononuclear carbocyclic aryl radical, Drepresents an organic radical selected from the group consisting of thelower alkyl and the mononuclear carbocyclic aryl series containing agroup taking part in the metal complex formation, X represents ametallisable group in o-position to the azo group selected from thegroup consisting of OH and COOH and: I a, 7 (130011 the chromium andcobalt complexes of said dyestufis.

2. A dyestuft selected from theclass consisting of the e a 7 OH Gmonoazo dyestufis having the formula:

OgN

f "'sotona V V V 7' 7 I i 5. The complex chromium compound of a monoazo7 ,7 dyestufi having the formula:

wherein A represents a mononuclearcarbocyclic aryl radical, D representsan organicradicalselected from the group consisting of lower alkyl andphenyl radicals whereby two carbon atoms should be between the amino andthe carboxyl group, X represents a metallisable group in o-position tothe azo group selected from the group consisting of OHand COOH, and thechromium and cobalt complexes of said dyestufis.

6. The complex chromium compound of a monoazo dyestuif having theformula:

SO2NH2 l5 7. The complex chromium compound of a monoazo dyestufi havingthe formula:

on NH-OHaCHzCOOH OzN 8. The complex chromium compound of "a monoazodyestufi having the formula:

COOH

NH OH SOaOaH! References Cited in the file of this patent UNITED STATESPATENTS

1. A DYESTUFF SELECTED FROM THE GROUP CONSISTING OF THE MONOAZODYESTUFFS HAVING THE FORMULA: